CN100517797C - Laminate, substrate with wiring, organic EL display element, connecting terminal of the element, and their manufacturing method - Google Patents

Abstract

A multilayer body which is used for formation of a base with wiring and comprises a conductor layer that is formed on a base and mainly contains Al or an Al alloy and a cap layer that is formed on the conductor layer and mainly contains an Ni-Mo alloy is disclosed. A base with wiring formed by etching the multilayer body to remove unnecessary metals and a method for manufacturing such a base are also disclosed.

Description

Matrix, organic EL display element, the splicing ear of organic EL display element and their manufacture method of layered product, band distribution

Technical field

The present invention relates to matrix, organic electroluminescent (EL) display element, the splicing ear of organic EL display element and their manufacture method of layered product, band distribution.

Background technology

As follow-on slim display element (FPD), organic EL display element begins to be applied to mobile phone etc.Organic EL display element has luminous organic material, shows by self-luminous.At aspects such as high-speed response, visibility, brightness, compare with in the past LCD and PDP, much good.

Its basic structure and operation principle for example can be referring to [Appl.Phys.Lett., 51,913 (1987)].Luminous in order to carry out, be to have organic horizons such as hole transporting layer, luminescent layer, electron supplying layer between transparent electrode (for example, tin-doped indium oxide (ITO)) and other the electrode from anode-side at least one side.Further study at present so that organic EL display element can long lifetime, high brightnessization, panchromaticization etc.

Organic EL display element is the display of current drive-type.Especially in organic EL display element of passive drive type, electric current only flows through in the selection phase of each row, and luminescent layer is luminous thus shows.Like this, compare with the LCD of voltage driven type, big electric current flows into electrode.

For example, anticipation is that 300 μ m * 300 μ m, anode number are 100 panel with 1/64 duty ratio driving Pixel Dimensions.Make luminous efficiency reach 1cd/A, and with mean flow rate 300cd/m ²Show that then the electric current summation at selection phase inflow negative electrode will reach 172.8mA.

For adapting to panchromaticization of thin-type display device (FPD) and the requirement of high definitionization in recent years, require the further low resistanceization of transparency electrode.But the low resistanceization of ITO that in the past was used for LCD etc. is near the limit.Therefore, introduced in the low resistive metal of extensive employings such as TFT-LCD and the low resistance distribution technology of ITO and usefulness.

Like this, between the negative electrode and splicing ear of organic EL display element, just need to adopt low resistance distribution technology to control the voltage rising that high-current leading rises.The following structure of general employing promptly is provided with auxiliary distribution between negative electrode and splicing ear, electric current is gone into splicing ear by the auxiliary ligand linear flow.

But, require the cry of panel maximization, high definitionization, high brightnessization very high.And will realize this goal, auxiliary distribution just must further low resistanceization.Generally, the low resistance wiring material of FPD often uses Al or Al alloy.But Al or the easy generation of Al alloy are separated out unusually, and easily form the Al oxide on the surface.In addition, even obtain to contact with other metal is electric, but the contact resistance height is difficult to direct use.

For this reason, the methods (for example, as the Japanese patent laid-open 13-311954 communique of example 1) in the past that cover Al or Al alloy with Mo or Mo alloy (alloy of Cr, Ti, Ta, Zr, Hf or V and Mo) that adopt more.This is because Mo and Al can use with a kind of etching solution etching.Like this, under the situation of Mo and Al combination, in being used to form the photic etching work procedure of display floater, Al and Mo can be formed pattern together.

But the moisture-proof of Mo is poor usually, is corroded by airborne moisture easily, if therefore the wiring material of FPD uses Mo, then has the problem of the easy deterioration of distribution.And if cover Al with the high Cr of moisture-proof, then can not use the etching solution etching identical with Al, be difficult in manufacturing process, form together pattern.

Even the Ni that moisture-proof is high places under super-humid conditions, resistance value is no change almost also.But, some etching solution (phosphoric acid: nitric acid: acetic acid: water=16: 1: 2: 1 (volume ratio)) be actually can not etching Ni (" photic etching and little processing ", 82～83 pages of the clear prestige integrated electronics of groove Gang publishing houses (distribution on May 10th, 1977)).

And Ni is a strong magnetic material, therefore is difficult to adopt the magnetron sputtering method as general one-tenth embrane method, so be difficult to the wiring material of Ni film as FPD.

In addition, in organic EL display element, the low resistance of the contact of negative electrode and auxiliary distribution and splicing ear and auxiliary distribution changes into and is new problem.Particularly the contact characteristic of negative electrode and auxiliary distribution not only must be a low resistance characteristic, also must be to also stablizing at the Joule heat that contact portion produces because of the electric current that flows into.

That is, contact resistance must not can rise because of Joule heat.It is generally acknowledged that contact resistance rise to be because of Joule heat owing to be used for that the oxidation of the metal of auxiliary distribution etc. causes.

Here, adopt the partial cross section figure of organic EL display element of prior art to see Figure 17.Anode 20a is set on transparency carriers such as glass 1.Being connected of the electrode of element internal and drive circuit adopts auxiliary distribution 30X to form.Pattern 30b and the 30a of inner pattern portion by the splicing ear side constitute.Negative electrode 70 connects with outside distribution 150 conductions that are connected by auxiliary distribution 30X.By input current between anode 20a and negative electrode 70, make organic EL layer 60 luminous.Counter substrate 80 is set, with organic EL layer 60 sealings such as grade.

Dielectric film 40 has the effect that picture is decided organic EL layer 60 and the contacted opening 40a of anode 20a, and in such structure, anode 20a uses ITO (indium oxide-tin oxide) usually, and negative electrode uses easily oxidized metals such as Al, Mg, Ag.Auxiliary distribution uses metals such as Cr.

In this case, if auxiliary distribution adopts for example Cr pattern of thickness 300nm, wide 150 μ m, long 4mm, resistivity 20 μ Ω cm, then its resistance value is 17.7 Ω, and the voltage that produces about 3.1V because of wiring resistance when aforesaid electric current is flow through descends, and rises from desired current potential.

Also have, as shown in figure 17,, form surface oxide layer, risen by this contact resistance that influences negative electrode 70 and auxiliary distribution 30X at auxiliary distribution 30X along with the carrying out of manufacturing process.And this voltage rising can cause demonstration inequality when tone shows, or causes the deterioration of others, as the puncture voltage rising of employed anode driver.

Here, the technology to the described auxiliary distribution of Japanese patent laid-open 11-317292 communique describes (example 2 in the past).This in the past the characteristics of example 2 be, use transparent electrode material at the splicing ear that links to each other with drive circuit, and cathode material is identical with the auxiliary ligand wire material.In this case, if cathode surface and auxiliary distribution surface do not have oxidizedly before being connected of cathode material and auxiliary ligand wire material, then can not produce the problem of the contact resistance of negative electrode and auxiliary distribution.

But the negative electrode of general organic EL display element uses the material of easy oxidation.Therefore be under the situation of same material at auxiliary distribution and negative electrode, in the manufacture process of organic EL display element, can produce the problem that auxiliary distribution surface is oxidized and contact resistance negative electrode increases.When particularly keeping at high temperature, contact resistance significantly rises.Use under the situation of Al and Al alloy at negative electrode and auxiliary distribution, remain on about 100 ℃, contact resistance significantly rises.

In addition, in Japanese patent laid-open 11-329750 communique (example 3 in the past), disclosed the technology of the contact resistance that is used to reduce negative electrode and auxiliary distribution.In the past in the example 3, form auxiliary distribution at this, adopt TiN or Cr, adopt Al, it is contacted with negative electrode, obtain low-resistance contact characteristic at electrode pattern in base pattern by minute base pattern and two patterns of electrode pattern.

But, in the past in the example 3, must form auxiliary distribution through the photic etching work procedure of secondary at this.And, use TiN as wiring material, in forming pattern, must adopt dry ecthing, therefore on production efficiency, have problems.And, when base pattern adopts Cr,, but being placed on the following time of high temperature about 100 ℃ even initial stage contact characteristic is good, contact resistance significantly increases.

In organic as previously mentioned EL display element, must make big electric current flow into electrode, negative electrode connect distribution the metal of handy low resistive form.Splicing ear portion but exposes to the open air under environment for use owing to be not at the element internal of sealing, and is therefore preferably environment resistant, particularly moisture-proof is good.

Like this, when the auxiliary ligand wire material is applied to organic EL display element, not only must excellent contact be arranged, and because extend to the sealed external of display floater, therefore also must farthest suppress corrosion that moisture causes etc. with negative electrode.

The objective of the invention is to obtain to be applicable to the layered product of organic EL display element, this layered product can basic comprising has the matrix of the band distribution of good moisture-proof, and its resistance is little and pattern forms function admirable.The invention provides the matrix of the band distribution that adopts this layered product formation.

The purpose of this invention is to provide the manufacture method of the matrix of making the band distribution and the matrix of band distribution obtained by this method, this manufacture method is to form the layered product that is specially adapted to FPD such as organic EL display element, can at an easy rate this layered product be carried out the etching of plane ground then.

The objective of the invention is to obtain as being used for organic EL display element, when input is used for luminous drive current, demonstrate the circuit structure of good low resistive in the contact site that constitutes the loop.And it can keep low resistance contact, and can realize having the contact characteristic of reliability the distribution electrode that big electric current flows into.The high organic EL display element of reliability that provides the corrosion resistance of the metal material that constitutes electrode and distribution to improve a lot.

The announcement of invention

Form 1 of the present invention is for providing a kind of layered product, it is the layered product that formation is with the matrix of distribution to use, the feature of this layered product is, has being the conductor layer 1 of principal component and being the top layer of principal component with the Ni-Mo alloy on conductor layer 1 with Al or Al alloy on the matrix.

Form 2 of the present invention between conductor layer 1 and matrix, begins successively have ITO layer and substrate layer from the matrix side for the layered product as form 1 record is provided.

Form 3 of the present invention is for providing the layered product as form 2 records, and the principal component of substrate layer is Mo or Mo alloy.

Form 4 of the present invention is for providing the layered products as form 2 or 3 records, and substrate layer is a principal component with NiMo, and contains and be selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

Form 5 of the present invention is for providing the layered product as each record in the form 2～4, and the containing ratio of the Ni in the substrate layer is 20～90 quality % of whole compositions, and the containing ratio of Mo is 10～80 quality % of whole compositions.

Form 6 of the present invention is for providing the layered product as each record in the form 1～5, between conductor layer 1 and top layer, have do not contain Ni prevent the Ni diffusion layer.

Form 7 of the present invention prevents that for the layered product as form 6 records is provided the Ni diffusion layer from being principal component with Mo, do not contain Ni.

Form 8 of the present invention prevents that for the layered product as form 6 or 7 records is provided the Ni diffusion layer from being MoNb, MoTa, MoV or MoW.

Form 9 of the present invention prevents that for the layered product as each record in the form 6～8 is provided the conductive material of Ni diffusion layer from containing Mo and Nb or Ta, and the containing ratio of Mo is 80～98 quality %, and the containing ratio of Nb or Ta is 2～20 quality %.

Form 10 of the present invention is for providing the layered product as each record in the form 1～9, and top layer contains and is selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

Form 11 of the present invention is for providing the layered product as each record in the form 1～10, and the containing ratio of the Ni in the top layer is 20～90 quality % of whole compositions, and the containing ratio of Mo is 10～80 quality % of whole compositions.

Form 12 of the present invention is for providing a kind of organic EL display element, it is the organic EL display element that adopts the layered product formation of each record in the form 1～11, the feature of this element is, on matrix, have and electrode layer 1 opposed electrode layer 2, between electrode layer 1 and electrode layer 2, disposed organic EL layer, begun to dispose successively matrix, conductor layer 1 and top layer from the matrix side.

Form 13 of the present invention is for providing a kind of organic EL display element, it is to have opposed electrode layer 1 and electrode layer 2 on matrix, between electrode layer 1 and electrode layer 2, disposed organic EL display element of organic EL layer, the feature of this element is, has the conductor layer 1 that is connected with electrode layer 1 conduction, upside at conductor layer 1 has top layer, and the principal component of conductor layer 1 is Al or Al alloy, and the principal component of top layer is the Ni-Mo alloy.

Form 14 of the present invention is for providing the organic EL display element as form 13 record, and top layer contains and is selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

Form 15 of the present invention for the organic EL display elements as form 13 or 14 records are provided, between conductor layer 1 and top layer, have do not contain Ni prevent the Ni diffusion layer.

Form 16 of the present invention is for providing the organic EL display element as each record in the form 13～15, prevents that the Ni diffusion layer from being to be selected among MoNb, MoTa, MoV, the MoW any.

Form 17 of the present invention is for providing the organic EL display element as each record in the form 13～16, has the substrate layer that contains Mo or Mo alloy at the downside of conductor layer 1.

Form 18 of the present invention is for providing the organic EL display element as each record in the form 13～17, and electrode layer 2 is the ITO layer.

Form 19 of the present invention is for providing a kind of splicing ear of organic EL display element, it is the splicing ear that is used to connect organic EL display element of electrode layer 1 on the matrix that is configured in organic EL display element and drive circuit, the feature of this splicing ear is, have with Al or Al alloy is the conductor layer 1 of principal component, with conductor layer 1 upside be the top layer of principal component with the Ni-Mo alloy, by by the requirement forming circuit of drive circuit to electrode layer 1 input current.

Form 20 of the present invention is for providing the splicing ear as organic EL display element of form 19 record, and top layer contains and is selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

Form 21 of the present invention for the splicing ear of organic EL display elements as form 19 or 20 records is provided, between conductor layer 1 and top layer, has do not contain Ni prevent the Ni diffusion layer.

Form 22 of the present invention is for providing the splicing ear as organic EL display element of each record in the form 19～21, flows to the requirement forming circuit of an electrode 1 by electric current from a plurality of electrodes 2, and the instantaneous maximum current that flows into an electrode layer 1 is more than the 50mA.

Form 23 of the present invention is for providing a kind of laminated body manufacturing method, and it is the laminated body manufacturing method of each record in the form 1～11, and the feature of this method is, forms the film of conductive layer 1 on matrix, forms the film of top layer then.

Form 24 of the present invention forms the film of transparent conductor layer 2 for the laminated body manufacturing method as form 23 records is provided, and forms pattern, forms the film of conductor layer 1 then.

Form 25 of the present invention when forming top layer, is carried out the processing of oxidation, nitrogenize, nitrogen carbonization, oxygen carbonization, nitrogen carbonization or the carbonization of oxygen nitrogen for the laminated body manufacturing method as form 23 or 24 records is provided.

Form 26 of the present invention is for providing a kind of matrix with distribution, and the feature of this matrix is, in form 1～11 on the layered product of each record with plane formation pattern.

Form 27 of the present invention is the manufacture method of splicing ear that a kind of organic EL display element is provided, it is the manufacture method of splicing ear of organic EL display element of each record in the form 19～22, the feature of this method is, form the film of transparent conductor layer 2, after forming pattern, formation contains the laminated film of conductor layer 1 and top layer, forms pattern then on laminated film.

Form 28 of the present invention is for providing a kind of manufacture method of organic EL display element, it is the manufacture method of organic EL display element of each record in the form 12～18, the feature of this method is, on matrix, form the film of transparent conductor layer 2, form the laminated film that contains conductor layer 1 and top layer then, as electrode 2, adopt the pattern of the requirement cambium layer press mold of laminated film with conductor layer 2 by at least a portion of the distribution from conductor layer 1 to splicing ear.

Form 29 of the present invention is for providing the manufacture method as organic EL display element of form 28 records, on matrix, form the film of transparent conductor layer 2, after forming patterns as electrode layer 2, the film by forming conductor layer 1 and the film of top layer and the cambium layer press mold forms pattern then on laminated film.

Form 30 of the present invention is for providing a kind of organic EL display element, and the feature of this element is to connect drive circuit on organic EL display element of each record in form 12～18, with 100cd/m ²Above brightness shows.

The simple declaration of accompanying drawing

Fig. 1 is the front view of the partial cut-out of an example of the matrix of the band distribution of employing layered product formation of the present invention.

Fig. 2 is the fragmentary cross-sectional view at the A-A ' of Fig. 1 cut-off rule.

Fig. 3 is the fragmentary cross-sectional view at the B-B ' of Fig. 1 cut-off rule.

Fig. 4 (a) is that the substrate of the band distribution of example 3 forms with the ESCA ANALYSIS ON DEPTH PROFILES figure of layered product before heat treatment.Fig. 4 (b) is that the matrix of the band distribution of example 3 forms with the ESCA ANALYSIS ON DEPTH PROFILES figure of layered product after heat treatment.

Fig. 5 (a) is the photo of observed result of the laser microscope of matrix behind anti-moisture test of the band distribution of the present invention of example 12.Fig. 5 (b) is the photo of observed result of the laser microscope of matrix behind anti-moisture test of the band distribution of example 15.

Fig. 6 is the plane graph of an example of organic EL display element of the present invention.

Fig. 7 is the fragmentary cross-sectional view at the C-C ' of Fig. 6 cut-off rule.

Fig. 8 estimates the plane graph of TEG for wiring resistance.

Fig. 9 is the plane graph of the TEG of the contact resistance of evaluation negative electrode and auxiliary distribution.

Figure 10 is the fragmentary cross-sectional view at the D-D ' of Fig. 9 cut-off rule.

Figure 11 is the current-voltage characteristic figure of the contact TEG that obtains at routine B2.

Figure 12 is the contact resistance of the contact TEG that obtains at routine B2.

Figure 13 is the current-voltage characteristic of the contact TEG that obtains at routine B3.

Figure 14 is the contact resistance of the contact TEG that obtains at routine B3.

Figure 15 is the photo of portion of terminal after hot and humid evaluation of organic EL display element of obtaining at routine B4.

Figure 16 is as a comparative example the photo of portion of terminal after hot and humid evaluation of organic EL display element among the example B4.

Figure 17 is the profile with the cathode contact portion of organic EL display element of prior art manufacturing.

Figure 18 is a plane graph of having implemented the portion of terminal of TCP encapsulation.

Figure 19 is the fragmentary cross-sectional view at the E-E ' of Figure 18 cut-off rule.

Figure 20 is the flow chart of the manufacture method of an example of the present invention.

Figure 21 is the profile of the configuration example 1 of layered product of the present invention.

Figure 22 is the profile of the configuration example 2 of layered product of the present invention.

Figure 23 is the stereogram of example of the substrate of band distribution of the present invention.

Figure 24 draws the fragmentary cross-sectional view of the formation operation 1 of circuit for the cathode side of organic EL display element.

Figure 25 draws the fragmentary cross-sectional view of the formation operation 2 of circuit for the cathode side of organic EL display element.

Figure 26 draws the fragmentary cross-sectional view of the formation operation 3 of circuit for the cathode side of organic EL display element.

Figure 27 draws the fragmentary cross-sectional view of the formation operation 4 of circuit for the cathode side of organic EL display element.

Figure 28 draws the fragmentary cross-sectional view of the formation operation 5 of circuit for the cathode side of organic EL display element.

Figure 29 is the simulation plane graph of the manufacturing process 1 of organic EL display element of the present invention.

Figure 30 is the simulation plane graph of the manufacturing process 2 of organic EL display element of the present invention.

Figure 31 is the simulation plane graph of the manufacturing process 3 of organic EL display element of the present invention.

Figure 32 is the simulation plane graph of the manufacturing process 4 of organic EL display element of the present invention.

Figure 33 is the simulation plane graph of the manufacturing process 5 of organic EL display element of the present invention.

The best mode that carries out an invention

Below, by drawings and Examples etc. embodiments of the present invention are described.These accompanying drawings, embodiment are example of the present invention, and scope of the present invention is not limited to this.As long as technology purport according to the invention, other execution mode also belongs to category of the present invention certainly.

Matrix used in the present invention is plane tabular not necessarily, can be curved surface, also can be difform.The for example available transparent or dense glass substrate of matrix, ceramic substrate, plastic base, metal substrate etc.

When being used for the organic EL display element from the luminous structure of matrix side, matrix is preferably transparent, and particularly glass substrate is more satisfactory on intensity and thermal endurance.The for example available water white soda lime glass substrate of glass substrate, quartz glass substrate, pyrex substrate, alkali-free glass substrate.When being used for organic EL display element, the thickness of glass substrate is preferably 0.2～1.5mm from intensity and transmitance.

The layered product that the matrix of band distribution of the present invention forms usefulness is must contain being the conductor layer of principal component and on the conductor layer being the layered product more than 2 layers of the top layer of principal component with the Ni-Mo alloy with Al or Al alloy (below be also referred to as Al be metal) on the matrix.Because conductor layer is that Al is a metal, therefore can make distribution is low resistance.Particularly the Al-Nd alloy can keep low resistance always, prevents separating out unusually of Al, and is therefore more satisfactory.The Al alloy is the alloy of Al and metals such as Nd, Ag, Cu, and preferably less existence can improve the metal of the problems such as resistance value of distribution.

At Al is in the metal level, can contain impurity Ti, Mn, Si, Cu, Na, O, and it is following more satisfactory that its content is aggregated in 1 quality %.Al containing ratio in the Al alloy-layer is preferably 80～100 quality % from reducing the resistance of distribution, more preferably 90～100 quality %.

In order to obtain sufficient conductivity and good pattern formation property, the thickness of conductor layer is 100～500nm more fortunately, and better at 100～400nm, that more better again is 150～400nm, and that good especially is 150～300nm.

The top layer that forms on conductor layer is to be the layer of principal component with the Ni-Mo alloy.The moisture-proof of Ni-Mo alloy-layer is good, so top layer is in the low-resistance while that keeps distribution, has that to be suppressed at Al be that the surface of metal level produces the Al oxide, prevents the function that contact resistance increases.

Therefore, adopt the unfailing performance of electronic installation of the matrix of the band distribution obtained to access raising.And the layered product that is obtained can form pattern with high precision.In addition, use photoetching process when the Ni-Mo alloy-layer forms pattern, can be with identical etching solution (acidic aqueous solution) with essentially identical speed etched conductors layer (Al is a metal level) and top layer (Ni-Mo alloy-layer).Promptly can form pattern together with conductor layer.

If the etching speed of conductor layer and top layer differs bigger, then when forming distribution, can cause over etching and produce residue, therefore undesirable.The etching speed of Ni-Mo alloy-layer can be adjusted by the ratio of components that changes Ni and Mo at an easy rate according to the kind of etching solution.The ratio of the relative Ni of Mo greatly then this etching speed is accelerated.

From moisture-proof and pattern formation property, the thickness of above-mentioned top layer is preferably 10～200nm, more preferably 15～50nm.

The containing ratio of Ni is preferably 20～90 quality % in the Ni-Mo alloy-layer, more preferably 55～75 quality %.If the containing ratio of Ni is less than 20 quality %, then the moisture-proof of Ni-Mo alloy-layer is insufficient, if surpass 90 quality % then the etching speed of etching solution is slow, is difficult to adjust to the degree identical with the etching speed of conductor layer.The containing ratio of Mo is preferably 10～80 quality % in the Ni-Mo alloy-layer, more preferably 20～40 quality %.

If the containing ratio of Mo is less than 10 quality %, then the etching speed of etching solution is slow, be difficult to adjust to the degree identical with the etching speed of conductor layer, then the moisture-proof of Ni-Mo alloy-layer is insufficient to surpass 80 quality %, and it is better that Ni in the Ni-Mo alloy-layer and the containing ratio of Mo add up to 90～100 quality % effects.

The Ni-Mo alloy-layer can contain in the metals such as Ti, V, Cr, Fe, Co, Zr, Nb, Ta, W more than a kind or 2 kinds, its content gets final product in the scope that can not make deteriorations such as moisture-proof, etching, for example below the 10 quality %.

The matrix of band distribution of the present invention forms with layered product and adopts sputtering method to form.Can be that target carries out the operation that sputter forms conductor layer in inert gas atmosphere with aluminium, and on this conductor layer, the operation of carrying out sputter formation top layer with Ni-Mo alloy system target form for example by on the surface that is combined in glass substrate.

Al is for example available Al metallic target of target, contains the Al alloys target of Nd, contains the non-alloys target of Al of Nd etc.The for example available Ni-Mo alloys target of Ni-Mo alloys target contains the Ni-Mo alloys target of Fe, contains the non-alloys target of Ni-Mo of Fe etc.

The non-alloys target of Ni-Mo that contains Fe also comprise for example will be littler than target area Ni plate, Mo plate, Fe plate be combined into the target that zyklopisch forms, and the target that Ni-Mo alloy target plate and Fe plate are combined to form.The matrix that can large tracts of land forms the band distribution of thickness homogeneous with sputtering method forms uses layered product.

The matrix that forms band distribution of the present invention forms the Al layer as conductive layer in the layered product of usefulness, during as the Ni-Mo alloy-layer of top layer, and for example can be with following method formation.

With Al is the negative electrode that target and Ni-Mo alloys target are installed in the magnetically controlled DC sputtering device respectively.Again matrix is installed on the substrate holder.Then, after the discharge of the gas in film forming room formation vacuum, import sputter gas Ar gas.Except that Ar gas, also can adopt He, Ne, Kr gas etc., but preferably discharge stability and inexpensive Ar gas.Sputtering pressure is preferably 0.1～2Pa.Back pressure is preferably 1 * 10 in addition ^-6～1 * 10 ^-2Pa.Substrate temperature is preferably room temperature～400 ℃.If the film-forming temperature height, then general resistance value reduces, and is therefore comparatively desirable.But surface roughness increases.In the time of must reducing surface roughness, better be to reduce substrate temperature.Reduce surface roughness, then have the advantage that the coverage of the Ni-Mo layer that makes the top that is formed at the Al layer improves.

When forming the Al metal level, use the Al metallic target, when forming the Al alloy-layer, Al and other the metal that forms alloy can be used separately as independent target and form alloy-layer, but controlled and homogeneity for the composition that improves conductor layer, preferably make the Al alloy of required composition in advance, used as target.

At first, by carrying out sputter, on matrix, form Al layer as conductor layer with the Al metallic target.Then, by being that target carries out sputter with Ni-Mo, form the Ni-Mo alloy-layer thereon, thereby form layered product.

Layered product of the present invention as mentioned above, it is the most basic having 2 layers on matrix, but is not limited to this, can also comprise the layered product more than 3 layers with other layer as described below.Other layer better also forms with sputtering method.

Layered product of the present invention can be to have the Ni of preventing diffusion layer between the Al metal level (conductor layer) of principal component at Ni-Mo alloy-layer (top layer) with Al or Al alloy, and this layer has the composition different with top layer.When top layer and conductor layer engaged, if heat-treat, then Ni diffused to conductor layer from top layer, and the resistance of conductor layer is increased.This prevents that the Ni diffusion layer from can prevent the increase of this resistance.This prevents that the also more handy sputtering method of Ni diffusion layer from forming.Be preferably in and form when in addition, preventing the Ni diffusion layer under the same condition of Al layer (sputter pressure etc.) and form.

The thickness that prevents the Ni diffusion layer forms property from block and pattern, is preferably 10～200nm, 15～80nm more preferably, and that good especially is 15～50nm.

For with top layer and conductor layer etching together, prevent that the Ni diffusion layer from better being is that the Mo of principal component is a metal level with Mo.With above-mentioned Mo is that metal level is as preventing that the Ni diffusion layer is formed between conductor layer and the top layer, in the pattern section portion after forming pattern, Mo exposes, but because Mo is the major part of metal level is covered by top layer and conductor layer, so can not hinder the raising of moisture-proof basically.

But, in order further to improve moisture-proof, prevent the Ni diffusion layer except Mo, can also contain in the metals such as Nb, Ta, V, W, Cr, Zr, Ti of 2～20 quality % one or more.If less than 2 quality %, then make the effect of moisture-proof raising insufficient by adding element, surpass then etching deterioration of 20 quality %, be unfavorable for making.The Mo that with Mo is principal component is that the containing ratio of Mo is preferably 80～98 quality % in the alloy-layer.

Top layer to layered product of the present invention preferably carries out processing such as oxidation, nitrogenize, oxynitriding, oxygen carbonization, nitrogen carbonization or the carbonization of oxygen nitrogen.Promptly when forming top layer, implement above-mentioned processing, form Ni-Mo alloy-layer, can prevent equally with the above-mentioned Ni of preventing diffusion layer that like this resistance from increasing the oxidation of Ni-Mo alloy-layer, nitrogenize, oxynitriding, oxygen carbonization, nitrogen carbonization or the carbonization of oxygen nitrogen etc.

This is handled and adopts when forming the Ni-Mo alloy-layer by sputter, with O ₂, N ₂, CO, CO ₂The mist of isoreactivity gas and Ar gas is implemented as the method for sputter gas.The containing ratio of reactant gas is preferably 5～50 volume %, more preferably 20～40 volume % from preventing the effect of Ni diffusion.

In addition, layered product of the present invention can have tin-doped indium oxide layer (ITO layer).In this case, be the big shortcoming of contact resistance of metal level and ITO layer owing to there is Al, so reality better is to form top layer/conductor layer/substrate layer/ITO layer/substrate across above-mentioned substrate layer.

Because the ITO layer can be used as transparency electrode, therefore in layered product of the present invention, when on substrate, forming formation substrate layer behind the ITO layer, conductor layer and top layer, if the zone that the shelter needs, then masked zone does not have substrate layer, conductor layer and top layer, has only the ITO layer.Used as electrode, when for example needing, can form organic horizon thereon, make organic EL display element.On the other hand, the zone of not sheltering forms substrate layer, conductor layer and top layer on the ITO layer, does not have jump ground as the ITO layer of electrode and substrate layer, conductor layer and top layer as distribution and links to each other.

The formation of ITO layer for example can adopt electronic beam method, sputtering method, ion plating method etc. to form the film of ITO layer on glass substrate.The ITO layer better uses SnO ₂Content be In ₂O ₃And SnO ₂The ITO target of 3～15 quality % of total amount, utilize sputtering film-forming.Sputter gas is preferably O ₂With the mist of Ar, O ₂Gas concentration is preferably 0.2～2 volume %.

The thickness of ITO layer is preferably 50～300nm, more preferably 100～200nm.

By utilizing sputtering method to form conductor layer and top layer again on this ITO film, the matrix that obtains having the band distribution of ITO layer forms uses layered product.

Owing to there is the big shortcoming of contact resistance of conductor layer and ITO layer, when therefore forming the ITO layer between matrix and conductor layer, the increase for the contact resistance that prevents ITO layer and distribution forms substrate layer under conductor layer.Substrate layer better is to be the layer of principal component with Mo or Mo alloy.With Mo or Mo alloy is that the layer of principal component is meant that the containing ratio of in layer Mo or Mo alloy is 90～100 quality %.Substrate layer is preferably under the condition identical with the Al layer (sputter pressure etc.) and forms.

From block and pattern formation property, the thickness of substrate layer is preferably 10～200nm, more preferably 15～50nm.

With Mo or Mo alloy be principal component the layer better be the Ni-Mo alloy-layer, when being substrate layer with the Ni-Mo alloy-layer, the Ni containing ratio of this alloy-layer is preferably 20～90 quality % of whole compositions, 55～75 quality % more preferably, the Mo containing ratio is preferably 10～80 quality % of whole compositions, more preferably 20～40 quality %.

Can also contain in the metals such as Ti, V, Cr, Fe, Co, Zr, Nb, Ta, W more than a kind or 2 kinds, its content gets final product in the scope that can not make deteriorations such as moisture-proof, etching, for example below the 10 quality %.

The composition of the substrate layer Ni-Mo alloy-layer that forms under conductor layer both can be identical with top layer, also can be different.If same composition, can adopt the target of identical material, good on the economy.Adjust the composition of Ni-Mo alloy-layer up and down, making etching speed is that the order of metal level (conductor layer), Ni-Mo alloy-layer (substrate layer) is accelerated successively by Ni-Mo alloy-layer (top layer), Al, when forming pattern, the pattern section shape can be processed into taper like this.This is more satisfactory to raising mar proof, zygosity.Can be provided with between the Ni-Mo alloy-layer of conductor layer and substrate layer and prevent the Ni diffusion layer.This prevent the Ni diffusion layer formation and above-mentioned be arranged between conductor layer and top layer prevent the Ni diffusion layer phase with.

If will with Mo or Mo alloy be principal component the layer be formed under the conductor layer as substrate layer, then in the pattern section portion after forming pattern, Mo exposes, but owing to covered by matrix or ITO film and conductor layer by the major part of the layer of principal component with Mo or Mo alloy, so can not hinder the raising of moisture-proof.

Do not form the above-mentioned Ni of preventing diffusion layer, by carrying out oxidation processes when the film forming, nitrogen treatment, carbonization treatment (perhaps their combination) also can form the layered product with desirable characteristics.The advantage of this situation is to form layered product with the less number of plies.

The advantage that forms the metal level press mold of 4 layers or 5 layers is to adopt the continuous film forming apparatus system of on-line to produce continuously.

Layered product of the present invention can have silicon dioxide layer between conductor layer and matrix.This silicon dioxide layer both can join with matrix, also can not join.This silicon dioxide layer adopts the titanium dioxide silicon target to carry out sputter usually and forms.At matrix is under the situation of glass substrate, can prevent that alkali composition in the glass substrate is transferred to conductor layer and makes the conductor layer deterioration.Thickness is preferably 5～30nm.

Layered product of the present invention is a low resistance, and pattern forms function admirable, and the moisture-proof height.If use this layered product to make the organic EL display,, therefore can obtain organic EL display element that the characteristics of luminescence of element long service life is improved then owing to can constitute with low resistance and the high distribution of reliability.Therefore, the layered product of the present invention that is obtained better forms the matrix of band distribution with the photoetching process etching.

To layered product, on its most surperficial top layer, be coated with photoresist, the copying Wiring pattern is removed unwanted part in the metal level according to the pattern of photoresist with etching solution, forms the matrix of band distribution.Etching solution better is an acidic aqueous solution, phosphoric acid, nitric acid, acetic acid, sulfuric acid, hydrochloric acid or their mixture, ammonium ceric nitrate, perchloric acid or their mixture.

Better be the mixed solution of phosphoric acid, nitric acid, acetic acid, sulfuric acid and water, be more preferably the mixed solution of phosphoric acid, nitric acid, acetic acid and water.

When forming the matrix of band distribution, each of layered product be (1) top layer/conductor layer/substrate layer for example, (2) top layer/conductor layer/substrate layer/ITO layer/substrate, (3) top layer/prevent Ni diffusion layer/conductor layer/prevent that each layer of Ni diffusion layer/substrate layer/ITO layer/substrate from utilizing etching solution to form same pattern.

When layered product has the ITO layer, can top layer/conductor layer and ITO layer be removed together with etching solution, also can remove top layer and conductor layer earlier, remove the ITO layer more in addition, perhaps can also earlier the ITO layer be formed pattern, sputter forms conductor layer and top layer again, removes distribution part top layer/conductor layer in addition then.

Then, use layered product of the present invention to form the preferable example that the matrix of being with distribution is made organic EL display element with accompanying drawing 1～3 explanation, but the present invention is not limited to this.

At first, on glass substrate 1, form the ITO film.Etching ITO film forms the ito anode 3 of band pattern.Then, form Ni-Mo alloy-layer (not having diagram), make it whole of cover glass substrate 1 by sputter.On this alloy-layer, by sputter form successively Mo as substrate layer be metal level (not having diagram), as the Al of conductor layer be metal level 2a, as the Mo that prevents the Ni diffusion layer be metal level (not having diagram), as the Ni-Mo layer 2b of top layer, obtain forming the layered product of usefulness with the matrix of distribution.Certain ITO film both can be formed at whole of glass substrate 1, also can be formed at a part.

On this layered product, be coated with photoresist, according to the pattern of photoresist, the unwanted part of etch metal layers, stripping photoresist, forming by Ni-Mo alloy-layer, Mo is that metal level, Al are that metal level 2a, Mo are the distribution 2 that metal level and Ni-Mo alloy-layer 2b constitute.Then, carry out ultraviolet irradiation and clean, whole layered product is carried out ultraviolet ray-ozone treatment or oxygen plasma treatment.Ultraviolet irradiation is cleaned and is removed organic substance with the ultra-violet lamp irradiation ultraviolet radiation usually.

Then, on ito anode 3, form organic horizon 4 with hole transporting layer, luminescent layer, electron supplying layer.When having cathode diaphragm (next door), before the vacuum evaporation of carrying out organic horizon 4, form the next door with photoresist.

After forming distribution 2, ito anode 3, organic horizon 4,, make it and ito anode 3 quadratures by the Al negative electrode 5 of sputter formation as the cathode back electrode.

Then, with the part that resin-sealed dotted line surrounded, form hermetically sealed can 6.

The matrix of band distribution of the present invention is owing to adopt above-mentioned layered product, promptly because conductor layer uses low-resistance Al or Al alloy, top layer uses the high Ni-Mo alloy of moisture-proof, so resistance is low, figure formation property is good, and the moisture-proof height, distribution can deterioration thus.

During matrix that layered product of the present invention is used as organic EL display element, must carry out the distinctive processing of organic EL to the matrix of band distribution, i.e. ultraviolet ray-ozone treatment, the matrix of band distribution of the present invention has tolerance to this processing, and is therefore more satisfactory.

The layered product of the application of the invention can form the matrix that low resistance, pattern form the high band distribution of function admirable and moisture-proof.Can make the high display of high definition and reliability.Particularly can be used in effectively and require the distribution low resistanceization to increase the service life organic EL display element of the raising characteristics of luminescence.

Below exemplify embodiment, various form of the present invention is described, but the present invention is not limited to this.

(embodiment)

Below describe the present invention in detail with embodiment.But the present invention is not limited to this certainly.

[comparative example 1-5]

Soda lime glass substrate to thick 0.7mm * long 100mm * wide 100mm cleans.Then, it is installed on the sputter equipment, uses the titanium dioxide silicon target, utilize the high frequency magnetron sputtering method on this substrate, to form the silicon dioxide layer of thick 20nm, obtain glass substrate with silicon dioxide layer.

Then, with ITO (SnO ₂Content be In ₂O ₃And SnO ₂10 quality % of total amount) target, utilize direct current magnetron sputtering process to form the ITO layer of thick 160nm, obtain glass substrate (also abbreviating substrate as) with the ITO layer.Sputter gas uses the O that contains 0.5 volume % ₂The Ar gas of gas.

Then, (annotate: remove the part that does not have film forming in order to keep substrate) on whole of the glass substrate of this band ITO layer, 5 kinds of targets with as shown in table 1 utilize direct current magnetron sputtering process, and 5 kinds of monofilms of formation obtain the overlay film glass substrate in Ar gas atmosphere.Back pressure is 1.3 * 10 ^{- 3}Pa, sputtering pressure are 0.3Pa, not heated substrates.The target thickness of Ni target is reduced to 1mm, makes it to carry out magnetron sputtering.

Measure the thickness of this overlay film glass substrate, film resistor, etching speed and moisture-proof (1) the results are shown in Table 1.

The Loresta IP MCP-T250 that film resistor uses Mitsubishi's oiling (strain) system measures according to 4 sonde methods.

Etching speed by phosphoric acid, nitric acid, acetic acid, and the volume ratio of water be followed successively by 16: 1: 2: in 1 the etching solution, with this overlay film glass substrate dipping 5 minutes, the time that is measured to the film dissolving tried to achieve.After 5 minutes, etching is also uncompleted to be evaluated as *.

Moisture-proof (1), is placed this overlay film glass substrate 1 day under the condition of 60 ℃-95%RH with constant temperature and humidity cabinet (エ ス ペ Star Network (strain) system, PR-1S), measures changes in resistance, estimates.The rate of change of film resistor is evaluated as more than zero, 5% less than 5% and is evaluated as *.

As known from Table 1, the moisture-proof of Mo layer is low, and the moisture-proof of Ni layer and Ni-Mo alloy-layer is good.Surface at the Mo layer can be visually observed corrosion.And be not visually observed corrosion on the surface of Ni layer and Ni-Mo alloy-layer.

Even flooding etching in 5 minutes, do not finish on the Ni layer yet.And the Ni-Mo alloy-layer with the Al layer with degree or to surpass its etching speed etched, etching performance is good.When particularly using the Ni-Mo-Fe alloys target, obtained almost identical etching speed with the Al layer.Therefore, among the embodiment afterwards, the formation service quality percentage of Mo alloy-layer is the Ni-Mo-Fe alloys target (back is also referred to as the Ni-Mo target) of 65%-32%-3%.To be called the Ni-Mo alloy-layer by the layer that the Ni-Mo target forms.

[routine 1-2]

Soda lime glass substrate to thick 0.7mm * long 100mm * wide 100mm cleans.Then, it is installed on the sputter equipment, uses the titanium dioxide silicon target, utilize the high frequency magnetron sputtering method on this substrate, to form the silicon dioxide layer of thick 20nm, obtain glass substrate with silicon dioxide layer.Then, on whole of the glass substrate of this band ITO layer, (annotate: remove the part that does not have film forming in order to keep substrate), use the Al metallic target, utilize direct current magnetron sputtering process, in Ar gas atmosphere, form Al layer (conductor layer).Back pressure is 1.3 * 10 ^-3Pa, sputtering pressure are 0.3Pa, not heated substrates.

On the substrate of the band conductor layer that obtains, use Mo target (example 1) or Ni-Mo target (example 2), utilize direct current magnetron sputtering process, in Ar gas atmosphere, form Mo layer (example 1) or Ni-Mo alloy-layer (example 2), obtain forming the layered product of usefulness with the substrate of distribution as top layer.Back pressure is 1.3 * 10 ^-3Pa, sputtering pressure are 0.3Pa, not heated substrates.The substrate of measuring the band distribution forms the thickness of the layered product of usefulness, moisture-proof (1), and film resistor and thermal endurance before this layered product heat treatment the results are shown in Table 2.

The evaluation and the reference example 1 of moisture-proof (1) carry out equally.When top layer is Mo layer (example 1), be visually observed corrosion, but top layer is not visually observed corrosion when being the Ni-Mo alloy-layer (example 2) on the surface on the surface.

Carry out the heat treatment of this layered product, that is, use thermostat (エ ス ペ Star Network (strain) system, PMS-P101), under air atmosphere, this layered product was placed 1 hour at 320 ℃.Measure the film resistor of this preceding layered product of this heat treatment, the resistance change rate (thermal endurance) before and after the heat treatment.Rate of change by film resistor is zero in the situation below 10%, surpasses 10% but be △ in the situation 100% below, 100% the situation of surpassing is * evaluation criterion estimate.

[example 3]

Whole (annotating: remove the part that does not have film forming in order to keep substrate) at the glass substrate of the band ITO of reference example 1 layer, use the Ni-Mo target, utilize direct current magnetron sputtering process, in Ar gas atmosphere, form Ni-Mo alloy-layer (substrate layer), obtain the glass substrate of belt material bottom.

Back pressure is 1.3 * 10 ^-3Pa, sputtering pressure are 0.3Pa, not heated substrates.Then, on this substrate layer with and the same method of example 2, form Al layer (conductor layer) and Ni-Mo layer (top layer), obtain layered product with the substrate formation usefulness of distribution.With the example 1 same thickness of measuring this layered product, moisture-proof (1), film resistor and thermal endurance before this layered product heat treatment the results are shown in Table 2.

The ESCA ANALYSIS ON DEPTH PROFILES figure of this layered product before and after the heat treatment of example 3 sees Fig. 4 (a) and (b).Hence one can see that, in this layered product of this example 3, because heat treatment Ni metal diffusing is to Al layer (conductor layer).

[routine 4-7]

On the substrate layer of the glass substrate of the belt material bottom of example 3, use the Mo target, utilize direct current magnetron sputtering process, in Ar gas atmosphere, formed Mo layer (preventing the Ni diffusion layer).Then, prevent on the Ni diffusion layer,, on this conductor layer, adopt and above-mentioned method and the condition that prevents that the Ni diffusion layer is same, formed Mo layer (preventing the Ni diffusion layer) with forming Al layer (conductor layer) with example 2 identical methods at this.

Prevent on the Ni diffusion layer at this, use the Ni-Mo target, employing and example 2 same method and conditions form Ni-Mo alloy-layer (top layer), obtain the substrate formation layered product with distribution.With the example 1 same thickness of measuring this layered product, moisture-proof (1), film resistor and thermal endurance before this layered product heat treatment the results are shown in Table 2.

Show that from table 2 and Fig. 4 (a) and (b) shown in example 1, top layer is that moisture-proof is poor under the situation of Mo, shown in example 2, under the situation for the Ni-Mo alloy-layer, moisture-proof is good.And for example shown in the example 3, if heat-treat under the state that Ni-Mo alloy-layer and Al layer join, then Ni is diffused into the Al layer, the thermal endurance deterioration.

On the other hand, from the result shown in the example 4～7 as can be known, if folder then can prevent stable on heating deterioration every the Mo layer between Ni-Mo alloy-layer and Al layer.The thickness of Mo layer can be more than 10nm, below the 60nm.

[routine 8-11]

Except replace Ar gas as being used to form the sputter gas of substrate layer and top layer with the mist of forming shown in the table 3, other adopts and example 3 same method and conditions are carried out sputter, and the substrate that has obtained the band distribution forms the layered product of usefulness.With the example 1 same thickness of measuring this layered product, moisture-proof (1), film resistor and thermal endurance before this layered product heat treatment the results are shown in Table 3.

As shown in Table 3, with nitrogenize of Ni-Mo alloy-layer or oxynitriding, can prevent that Ni from being the metal level diffusion to Al, thereby prevent the thermal endurance deterioration.

[example 12]

Using width/spacing is the mask pattern of 25 μ m/65 μ m, the substrate of the band distribution of example 5 is formed use layered product, utilizes photoetching process, forms pattern with the Al etching solution, forms the substrate of being with distribution.With the example 1 same thickness of measuring this layered product, form the preceding film resistor of pattern, and the resistance change rate (thermal endurance) before and after this layered product heat treatment, the results are shown in Table 4.

Pattern formation property surpasses pattern formation line institute reach by measuring etching from the sideline with right angle orientation, has observed over etching.By over etching is that situation below the 2 μ m is zero, the situation that surpasses 2 μ m for * evaluation criterion estimate.

The moisture-proof (2) of substrate that forms the band distribution behind the pattern, is placed the substrate of this band distribution 1 day under the condition of 60 ℃-95%RH by with constant temperature and humidity cabinet (エ ス ペ Star Network (strain) system, PR-1S), estimates with laser capture microdissection sem observation distribution.By what do not find at distribution to corrode is zero, find corrosion for * evaluation criterion estimate.The evaluation result of pattern formation property, moisture-proof (2) sees Table 4.In addition, the observed result (500 times of multiplying powers) of the laser microscope after the evaluation of the moisture-proof (2) of the substrate of the band distribution of example 12 is seen Fig. 5 (a).

[example 13]

Whole (annotating: remove the part that does not have film forming in order to keep substrate) of the glass substrate of the band ITO of reference example 1 layer, use the Ni-Mo target, utilize direct current magnetron sputtering process, at the Ar-CO that forms shown in the table 4 ₂Form Ni-Mo alloy-layer (substrate layer) in the mixed-gas atmosphere.Back pressure is 1.3 * 10 ^-3Pa, sputtering pressure are 0.3Pa, not heated substrates.

Then, on this substrate layer, use the Al metallic target to form Al layer (conductor layer), use the Mo target to form Mo layer (preventing the Ni diffusion layer) on this conductor layer, prevent to use on the Ni diffusion layer Ni-Mo target to form Ni-Mo alloy-layer (top layer) at this again, the substrate that has obtained the band distribution forms the layered product of usefulness.With the example 1 same thickness of measuring this layered product, the film resistor before pattern forms, and the resistance change rate (thermal endurance) before and after this layered product heat treatment the results are shown in Table 4.

Then, adopt with example 12 identical method and conditions and form pattern, obtained the substrate of band distribution.With example 12 same pattern formation property and the moisture-proofs (2) of measuring the substrate of this band distribution, its evaluation result sees Table 4.Remove to place 5 beyond the highest heavens, the same moisture-proof (3) to the matrix that layered product formed the band distribution behind the pattern of other and moisture-proof (2) is estimated, and it the results are shown in Table 5.

[example 14]

Whole (annotating: remove the part that does not have film forming in order to keep substrate) of the glass substrate of the band ITO of reference example 1 layer, use the Ni-Mo target, utilize direct current magnetron sputtering process, at the Ar-CO that forms shown in the table 4 ₂Formed Ni-Mo alloy-layer (substrate layer) in the mixed-gas atmosphere.Back pressure is 1.3 * 10 ^-3Pa, sputtering pressure are 0.3Pa, not heated substrates.Then, on this substrate layer, use the Al metallic target to form Al layer (conductor layer).

On this conductor layer, utilize direct current magnetron sputtering process again, use the Ni-Mo target, at the Ar-CO that forms shown in the table 4 ₂Form Ni-Mo alloy-layer (top layer) in the mixed-gas atmosphere, the substrate that has obtained the band distribution forms the layered product of usefulness.With the example 1 same thickness of measuring this layered product, film resistor before pattern forms and the resistance change rate (thermal endurance) before and after this layered product heat treatment the results are shown in Table 4.

Then, adopt with example 12 identical method and conditions and form pattern, obtained the substrate of band distribution.With example 2 same pattern formation property and the moisture-proofs (2) of measuring the substrate of this band distribution, its evaluation result sees Table 4.

[example 15]

Whole (annotating: remove the part that does not have film forming in order to keep substrate) of the glass substrate of the band ITO of reference example 1 layer, use the Mo target by direct current magnetron sputtering process, in Ar gas atmosphere, formed the Mo layer.Back pressure is 1.3 * 10 ^-3Pa, sputtering pressure are 0.3Pa, not heated substrates.

Then, use the Al metallic target to form Al layer (conductor layer) on this substrate layer, form Mo layer (top layer) with the Mo target again on this conductor layer, the substrate that has obtained the band distribution forms the layered product of usefulness.With the example 1 same thickness of measuring this layered product, film resistor before pattern forms and the resistance change rate (thermal endurance) before and after this layered product heat treatment the results are shown in Table 4.

Then, adopt with example 12 identical method and conditions and form pattern, obtained the substrate of band distribution.With example 12 same pattern formation property and the moisture-proofs (2) of measuring the substrate of this band distribution, its evaluation result sees Table 4.In addition, the observed result (500 times of multiplying powers) of the laser microscope after the evaluation of the moisture-proof (2) of the substrate of the band distribution of example 15 is seen Fig. 5 (b).

From table 4 and Fig. 5 (b) as can be known, when top layer was the Mo layer, moisture-proof was poor.

[example 16]

Prevent that except not forming the Ni diffusion layer, other employing is carried out sputter with example 13 identical method and conditions, forms layered product of the present invention.With the example 1 same thickness of measuring this layered product, film resistor before pattern forms and the resistance change rate (thermal endurance) before and after this layered product heat treatment the results are shown in Table 4.

Then, adopt with example 13 identical method and conditions and form pattern, formed the substrate of band distribution.With example 13 same pattern formation property, moisture-proof (2) and the moisture-proofs (3) of measuring the substrate of this band distribution, it the results are shown in Table 5.Moisture-proof (2) is one day, and moisture-proof (3) is continuous 5 days test.In the table, zero for there not being corrosion, and △ is for there being corrosion slightly, * for corrosion is arranged.

[example 17]

Except the containing ratio with Nb is that the Mo-Nb alloys target of 5 quality % forms and to prevent the Ni diffusion layer, prevent that the Ni diffusion layer from adopting beyond the MoNb alloy-layer, other is with carrying out sputter with example 13 identical method and conditions, the formation layered product.With the example 1 same thickness of measuring this layered product, film resistor before pattern forms and the resistance change rate (thermal endurance) before and after this layered product heat treatment the results are shown in Table 4.

Then, adopt with example 13 identical method and conditions and form pattern, obtained the substrate of band distribution.With example 13 same pattern formation property, moisture-proof (2) and the moisture-proofs (3) of measuring the substrate of this band distribution, it the results are shown in Table 5.

[example 18]

Except the containing ratio with Nb is that the Mo-Nb alloys target of 10 quality % forms and to prevent the Ni diffusion layer, prevent that the Ni diffusion layer from adopting beyond the MoNb alloy-layer, other with and example 13 identical method and conditions carry out sputter formation layered product.With the example 1 same thickness of measuring this layered product, film resistor before pattern forms and the resistance change rate (thermal endurance) before and after this layered product heat treatment the results are shown in Table 4.

Then, adopt with example 13 identical method and conditions and form pattern, obtained the substrate of band distribution.The pattern of having measured the substrate of this band distribution with example 13 equally forms property, moisture-proof (2) and moisture-proof (3), and it the results are shown in Table 5.

As known from Table 5, prevent that the Ni diffusion layer from adopting the MoNb alloy, can further improve moisture-proof.

[example 19]

Except making substrate temperature is 200 ℃, other has obtained layered product with carrying out sputter with example 13 identical method and conditions.With the example 13 same thickness of measuring this layered product, the film resistor before pattern forms, thermal endurance, pattern formation property, moisture-proof (2) and moisture-proof (3), it the results are shown in Table 5.

Surface roughness (Ra) is measured with atomic force microscope (Digital Instruments corporate system, NanoScope IIIa), and the Ra of example 13 is 3nm, and the Ra of example 19 is 21nm.Thus the result as can be known, heated substrates can make resistance value reduce.On the other hand, heated substrates can make surface roughness increase.

In above-mentioned example, carry out under the situation of oxidation, nitrogenize, carbonization, oxynitriding, nitrogen carbonization, oxygen nitrogen carbonization treatment, the containing ratio of this atom in formed metal film generally for example is number %～about 30%.

The fragmentary cross-sectional view of layered product of the present invention is seen Figure 21, Figure 22.Figure 21 is the figure of 3-tier architecture for the laminated film 35 of expression layered product.For example, NiMo-O _x/ Al is metal/NiMoN _yLayer structure.Figure 22 is the figure of 4 layers of structure for presentation layer press mold 35.For example, NiMo-O _x/ Al is metal/Mo/NiMo or NiMo-O _x/ Al is the layer structure of metal/MoNb/NiMo.As described above in Example, also comprise the layered product that laminated film is 5 layers of structure.For example, NiMo-O _x/ Mo/Al is the layer structure of metal/Mo/NiMo.

Figure 23 is near the simulation drawing of the state the splicing ear of the organic EL display element of expression.Link to each other with splicing ear of the present invention from the connection of outside lead-in wire 41.The following describes the Embodiment B 1～B4 that forms organic EL display element.Example B1～B4 is organic EL display element of passive drive type, but also is applicable to the driving organic EL display element of TFT of the electrode that uses low resistive certainly.

[routine B1]

Fig. 6 is the plane graph of an example of organic EL display element of the present invention.Fig. 7 is the C-C ' section of Fig. 6.In Fig. 6, omitted the diagram of counter substrate and TCP.Figure 20 is the flow chart of the manufacture method of organic EL display element of the present invention.Following with reference to Fig. 6,7, describe by the sequence of steps of Figure 20.

The part sectioned view of the pairing organic EL display element of each step is seen Figure 24～Figure 28, and plane graph is seen Figure 29～Figure 33.In this example, at first form nesa coating (ITO film) on substrate, pattern-making forms the electrode layer as anode 20a.This anode distribution splicing ear 20b is positioned at the end on the substrate.Then, on whole base plate face nearly, form the laminated film 35 (Figure 29) of metal.With laminated film 35 pattern-makings, form auxiliary distribution 30 (Figure 30) thereafter.

Form pixel openings 40a of portion and dielectric film 40 (Figure 31), the part relevant with demonstration with dielectric film 40 covering anode 20a makes it to cover the whole base plate face that comprises auxiliary distribution 30 and anode 20a.Form pixel openings 40a of portion and dielectric film patterns of openings 40b (Figure 32).Form the metal pattern of negative electrode 70 again, be connected, and make its contact with these parts (Figure 33) with auxiliary distribution 30.The end of auxiliary distribution forms splicing ear side pattern, is connected with outside drive circuit.

The pattern that layered product of the present invention can carry out anode earlier forms, and forms the laminated film (with reference to Figure 29) of metal thereafter on real estate.Perhaps, also can suitably form required film according to the zone of real estate.

At first, according to step S1, on the silica dioxide coating of glass substrate 1, form conductive film with silica dioxide coating.This conductive layer is equivalent to above-mentioned electrode layer 2.Glass substrate is available bases soda lime glass for example.The thickness of silica dioxide coating is generally 5～30nm, for example can use sputtering film-forming.

This conductive layer generally has light transmission.Having light transmission and be meant as so-called transparent conductivity layer, remove the transmitance height of light, is beyond 90～100%, can also have the transparency to a certain degree.Electrode layer 2 better is the transparent conductivity layer.Because this can give full play to the function as display element.

The thickness of conductive layer is generally 50～300nm, is preferably 100～200nm.Relatively be typically the ITO film that adopts the DC sputtering method to make.Use the ITO film in this example.In addition, conductive layer generally can adopt the manufacturing of physical vapor growth methods (PVD) such as vacuum vapour deposition, ion plating method.

Then, according to step S2, in photic etching work procedure photoresist is formed pattern, thereafter according to step S3, etching ITO film then according to step S4 stripping photoresist, obtains anode 20a and anode distribution splicing ear 20b.Only otherwise influence technology purport of the present invention, photoresist can adopt any known photoresist.Etching for example can be used the mixed aqueous solution of hydrochloric acid and nitric acid.Only otherwise influence technology purport of the present invention, peeling off of photoresist can be used any known remover.

Then,, for example adopt the DC sputtering method, form the metal level press mold that the conductive formation that contains Al or Al alloy reaches the top layer that is formed by the Ni alloy according to step S5.Making distribution is low resistance, and the most handy Al of conductive formation forms.In this case, for improving corrosion resistance, also can use Al alloys such as AlNd and AlSiCu.Detailed film forming for example back is described.

Thereafter, according to step S6, form the photoresist pattern in photic etching work procedure, then according to step S7, etching lamination metal film is according to step S8 stripping photoresist.Only otherwise influence technology purport of the present invention, photoresist in this case also can use any known photoresist.

The etching solution that etching for example can use the mixed aqueous solution by phosphoric acid, hydrochloric acid, nitric acid to constitute.Only otherwise influence technology purport of the present invention, peeling off of photoresist can be used any known remover.Laminated film of the present invention can carry out etching together with this etching solution, forms auxiliary distribution 30 thus.Formation is positioned at the private side drafting department 30a and the splicing ear side drafting department 30b of element inboard.

(the step S2～S4) and the pattern of lamination metal film form operation (step S6～S8) also can not adopt the pattern of above-mentioned ITO film to form operation, and adopt sputtering method to form ITO film and lamination metal film successively, successively lamination metal film and ITO film are formed figure thereafter.But, after forming, the pattern of auxiliary distribution carries out under the etched situation of ITO, because the etching solution of ITO is a strong acid, if there is pore in photoresist, then the auxiliary ligand line pattern might disappear, and it is more satisfactory therefore to carry out the manufacture method that the pattern of ITO forms earlier.

Thereafter, according to step S9, spin coating for example the photosensitive polyimide film as dielectric film, according to step S10, in photic etching work procedure, behind the formation pattern, solidify according to step S11, shown in Fig. 6,7, obtain having the insulating film pattern 40 of the 40a of pixel openings portion in pixel portions.The thickness of the insulating film pattern 40 after the curing is generally about 1.0 μ m.When pixel openings portion was the 300 μ m * 300 μ m left and right sides, the contact formation portion of negative electrode and auxiliary distribution was preferably in 200 μ m * below the 200 μ m, can not influence the size of whole display element like this.

Thereafter, according to step S12, for example spin coating photonasty acrylic resin behind the formation pattern, solidify to form negative electrode and separates pattern 50 (with reference to Fig. 9) in photic etching work procedure.When forming this negative electrode separation pattern, preferably use negative interaction type photoresist, make it be the back taper structure.During from top irradiates light, dark place is solidified insufficient more, just has the sectional area below structure narrower than the top of cured portion when the result sees from above.Here it is refers to have the back taper structure.

If this back taper structure is set, in operation thereafter, when the mask evaporation of negative electrode, can evaporation not dark part just to seeing from above.Can carry out the mutual separation of negative electrode thus.Above-mentioned photosensitive polyimide resin, photonasty polyacrylic resin are interchangeable sometimes.In addition, only otherwise influence technology purport of the present invention, can also use epoxy resin, any known dielectric film resin such as phenolic resins.

Thereafter, according to step S13, for example adopt parallel flat RF plasma (high-frequency plasma) device, the irradiation of enforcement oxygen plasma, carry out the surface modification of ITO film, then according to step S14, for example adopt evaporation coating device, mask evaporation organic EL layer 60 and negative electrode 70 are (with reference to Figure 27～Figure 28 and Figure 29～Figure 33).

This negative electrode is equivalent to electrode layer 1 of the present invention.Organic EL layer is many to be inscape with boundary layer, hole transporting layer, luminescent layer, electron injecting layer etc.But also can use different therewith layer structures.The thickness of organic EL layer is generally 100～300nm.

By forming this insulating film pattern, the end of anode 20a is insulated film and covers.Thus, with the face planarization that organic EL layer and anode 20a join, electric field is concentrated wait the possibility of the broken string of the organic EL layer that causes or negative electrode to reduce, the insulation voltage of anode and negative electrode improves.Use Al at negative electrode more.But the alloy that also can use alkali metal, Ag, Ca, Mg, Y, In such as Li and comprise them replaces Al.

The thickness of negative electrode is generally 50～300nm.Need not negative electrode and contain Al or Al alloy all, Al or Al alloy are better contained in the position that conductive layer is connected with aforementioned auxiliary distribution.In addition, negative electrode can also adopt the manufacturing of physical vapor growth methods (PVD) such as sputtering method, ion plating method sometimes.

Thus, form organic EL pattern 60 and the negative electrode pattern 70 (with reference to the plane graph of Fig. 6) that constitutes by organic EL layer.By using laminated film of the present invention at auxiliary distribution and cathode terminal portion, can be low resistance, can target and the drive circuit splicing ear keep low contact resistance, and can obtain to contain organic EL display element of auxiliary distribution and be used to drive its drive circuit with the high contact characteristic of reliability.

Thereafter, step S15 is will be as the CaO that the catches water material 100 mixing film that forms in the resin of going into of fitting in counter substrate 80.For this reason, counter substrate 80 is preferably formed as the structure that glass substrate is partly cut out with sanding machine.Then, behind the periphery of device substrate coating ultraviolet curing resin and counter substrate 80 fit, irradiation ultraviolet radiation forms periphery sealing 90, fixedly counter substrate 80.These operations should be implemented under blanket of nitrogen, in order to avoid moisture and oxygen are sneaked in the display floater.Then, cut off substrate, be separated into each panel, and package terminal portion is exposed.

Then, step S16 is for externally encapsulating drive circuit.Specific practice is, in the splicing ear side pattern 30b applying anisotropic conductive film 110 as splicing ear, disposes the Copper Foil distribution of TCP then, and it is overlapping to make terminal and TCP side be connected distribution, fits by thermo-compressed then.

Here with reference to Figure 17, sealing process important in the manufacture process of organic EL display element and packaging process thereafter are described.Because moisture can make organic LED element deterioration, therefore with periphery sealing 90 sealing counter substrate 80.Used in this case sealant is preferably photonasty epoxy resin.

What then, organic EL display element is described catches the water material.In organic EL display element, catch the water material in order when sealing, to remove moisture, preferably to add.Catch the water material and can use barium monoxide, calcium oxide, zeolite etc.For example, go into the recess (with reference to Figure 17) that water material membrane 100 is bonded in the inner face side of counter substrate 80 of catching that forms in the resin molding with calcium oxide is mixing.

Connect anode and negative electrode and external drive circuit thereafter.Then, at anode and the TCP of cathode terminal portion encapsulation drive circuit.The method of attachment of organic E1 display element and drive circuit is connected it for the terminal that is connected with distribution conduction in the element is set with drive circuit.

Highdensity connection can adopt the drive circuit with the outside to be connected with the side that the Copper Foil distribution has formed the polyimide film of pattern, the opposing party is connected (TCP encapsulation) by anisotropic conductive film (ACF) with the element terminal, or on the drive circuit bare chip, au bump is set, be connected the method for (COG encapsulation) with terminal by ACF.

TCP is meant drive IC and connects mode on the films such as being arranged on polyimides with distribution.Portion of terminal plane graph through the TCP encapsulation is seen Figure 18, and the section of E-E ' cut-off rule of Figure 18 is seen Figure 19.On glass substrate 1, form terminal 30, the anisotropic conducting film (ACF) 110 of fitting thereon, the connection distribution 150 that will be formed at from it again on the polyimide film of TCP12 is adjusted according to terminal, fits then.Anisotropic conducting film is dispersed electro-conductive particulate 130 and the film that forms in resin.General resin adopts epoxy resin, and electrically conductive particles adopts particulate that is coated with Ni, Au formation on plastics or the particulate that has used the Ni particle.

TCP is with drive IC 140 and connects distribution 150 and be formed at encapsulation on the polyimides 160.Connect the distribution 150 main Cu of use.In the TCP connection procedure at first in portion of terminal with the temporary transient crimping of ACF.At this moment temperature is at 50～150 ℃, and pressure is generally 1～2MPa.

Adjust the position relation of connection distribution 150 and the terminal 30C of TCP, with TCP final crimping thereafter.At this moment temperature is at 150～250 ℃, and pressure is generally 2～3MPa.After the final crimping, be present in the crushed dispersion of electrically conductive particles that connects between distribution 150 and the terminal 30C, obtain conduction thus and connect.After encapsulation is finished, also can adopt with the resin-coating encapsulation to prevent corroding method.General silicones or the UV solidified type epoxy resin etc. of adopting.

Make organic EL display element as mentioned above.On the other hand, for the function of confirming indivedual positions and the performance of grasping each operation, form test element group (hereinafter referred to as TEG) sometimes.The TEG that produces equally with said process sees Fig. 8 and Fig. 9.

They are formed by a part of constituent material, and the whole operations before the S15 in Figure 20 form.Thus, can not only be to the performance and the processability of material, and can also estimate by the influence of technical process to material.In Fig. 8, remove the ITO film by S1～S8 step etching, thereafter, form pattern as the auxiliary distribution 30 of metal level press mold.Can know resistance by this pattern by the film formed distribution of lamination.Here, the distribution width is 40 μ m, and the length of distribution is 6.8mm.Fig. 9 forms by S1～S14 step.The section of D-D ' cut-off rule of Fig. 9 is seen Figure 10.

At first remove the ITO film by S1～S4 step.Form auxiliary distribution 30 by S5～S8 step with the pattern of laminated film then, then form the patterns of openings 40b of insulating film pattern 40 and dielectric film by S9～S11 step.The dielectric film patterns of openings is the square of a length of side 200 μ m.According to S12 step form negative electrode and separate pattern 50 thereafter.This pattern has slit 50a near the dielectric film opening.

Then, by the pattern of S14 step formation negative electrode 70, finish TEG.In this TEG, the pattern of the laminated film of metal, promptly auxiliary distribution 30 is connected with negative electrode pattern 70 at dielectric film peristome 40b.When the auxiliary distribution (pattern of laminated film) 30 of adjacency applied voltage, electric current flowed into the negative electrode pattern from above-mentioned patterns of openings 40b, flowed into the auxiliary distribution (pattern of laminated film) 30 of adjacency again through the slit 50a of partition pattern.

At this moment, electric current flows at the connecting portion of two metal patterns (part of laminated film) and negative electrode pattern, and the resistance of deduction other parts just can be calculated the resistance (contact resistance) at junction surface.Here, be provided with negative electrode separate pattern be because when negative electrode separates the pattern video picture because developer solution accumulates at dielectric film patterns of openings 40b etc., may influence contact resistance, must verily reproduce this situation.Can estimate the contact resistance of wiring resistance, auxiliary distribution and cathodic metal by these.

According to above-mentioned explanation, made organic EL display element.The content of each operation, short of special description, same as described above.

[routine B2]

According to above-mentioned explanation, Fig. 8, Fig. 9 and wiring resistance TEG and contact resistance TEG shown in Figure 10 have been made.At first, according to S1～S4, formed the ITO film of 150nm, and etching is removed.Utilize DC sputtering method successively with NiMo, Mo, Al, Mo, NiMo film forming thereafter.Make as substrate layer. the NiMo film forming time, import CO ₂Carry out the oxygen carbonization treatment.

The thickness of each film is that the NiMo layer is 50nm, and Mo is 20nm, and the Al layer is 400nm.This laminated film phosphoric acid, acetic acid, aqueous solution of nitric acid etching together.Obtain lamination metal pattern 3 thus.Obtain insulating film pattern 40 thereafter.At this moment, in Fig. 8, do not form insulating film pattern.Obtain negative electrode then and separate pattern 50.With aforementioned same, in Fig. 8, do not form negative electrode and separate pattern.At this moment the slit 50a that negative electrode separates pattern is 300 μ m.

Then, use parallel flat RF plasma device, under the surface modification condition of ITO film, carried out the oxygen plasma irradiation.Concrete way is that at oxygen flow 50sccm (50mL/min under the standard state), the total pressure 6.7Pa of gas under the plasma treatment condition of 1.5kW, has carried out the plasma treatment of 60 seconds RIE (reactive ion etching) mode.

Then, use evaporation coating device, mask evaporation 300nm has obtained negative electrode pattern 70 as the Al of negative electrode.Measured the above-mentioned wiring resistance TEG that makes with 4 terminal methods, the result is 25.5 Ω.It is converted into film resistor then is 0.15 Ω/.Film resistor after the firm sputter of this film is 0.13 Ω/.

Hence one can see that, through the manufacture process of organic EL display element, though resistance rises to some extent, but still forms low-resistance distribution.The current-voltage characteristic of contact TEG is seen Figure 11, and contact resistance is seen Figure 12.Contact resistance is that the resistance that obtains deducts the resistance that resistance obtained under the distribution part normal temperature.

Use probe to apply voltage at the contiguous metal pattern of TEG, probe and terminal are contacted under 4.8V, terminal burns fully as a result, therefore can not apply the voltage above this value.Known to the measurement result, can infer above-mentioned 5 when press mold is used for auxiliary distribution layer by layer, contact resistance is low, is 0.5～3.0 Ω, and the electric current that flows through can be more than 350mA.Here to reach maximum gradually be because distribution part is heated because of electric current flows through to current value, and temperature rises, and causes that resistance value rises.

Make identical pattern with Cr, and estimate, though the result can be suppressed at contact resistance about 10 Ω, when the electric current that flows through about 10mA, pattern burns fully in contact portion.

As mentioned above, if above-mentioned lamination metal film is applied to the auxiliary distribution of organic EL display element, then to compare with used in the past Cr, low resistance and contact resistance are low, can flow into big electric current, the display that can produce high brightness and can carry out the demonstration of high duty.

[routine B3]

The metal level press mold and the routine B1 that use other have made TEG equally.Used metal level press mold is for successively with NiMo, Al, the formed laminated film of NiMo film forming.When forming the NiMo film of substrate layer, input CO ₂Carry out the oxygen carbonization, input N when the NiMo of top layer film forming ₂, carry out nitrogenize.The thickness of each film is that the NiMo layer is 50nm, and the Al layer is 400nm.Other operation is identical with routine B1.

Measured the above-mentioned wiring resistance TEG that makes with 4 terminal methods, the result is 18.7 Ω.It is converted into film resistor then is 0.11 Ω/.The current-voltage characteristic of contact TEG is seen Figure 11, and contact resistance is seen Figure 12.Under this routine situation, even apply 4.2V, be applied to positive distribution and burnt fully, therefore can not apply the voltage above above this value.If this lamination metal film is applied to the auxiliary distribution of organic EL display element, then can produce identical with routine B1 or the high performance display that surpasses it.

[routine B4]

According to above-mentioned explanation, organic EL display element and TEG have been made.Manufacture process about TEG is omitted.The plane graph of organic EL display element of this example is seen Fig. 6, and C-C ' section is seen Fig. 7.

At first, be on the silica dioxide coating of soda lime glass substrate 1 of 0.7mm at the thickness of the silica dioxide coating of the 200nm that contains useful sputtering film-forming, adopt the DC sputtering method to form the ITO film of 150nm.Then, in photic etching work procedure photoresist is formed pattern, thereafter with the mixed aqueous solution etching ITO film of hydrochloric acid and nitric acid, stripping photoresist then obtains the pattern of anode 20a and anode distribution splicing ear 20b.

Photoresist uses novolac resin, and light carving rubber stripper uses monoethanolamine., utilize DC sputtering method, formed the lamination metal film that constitutes by NiMo, Al, Mo, NiMo successively thereafter.The thickness of this lamination metal film is that the NiMo layer is 50nm, and the Mo layer is 20nm, and the Al layer is 360nm.Here, by input CO ₂NiMo film to substrate layer has carried out the oxygen carbonization.

, in photic etching work procedure, form the photoresist pattern thereafter, then use the etching solution etching lamination metal film that the mixed aqueous solution by phosphoric acid, hydrochloric acid, nitric acid constitutes after, peeled off photoresist.Thus, form as the private side drafting department 30a and the splicing ear side drafting department 30b that assist distribution 30.Photoresist uses novolac resin, and light carving rubber stripper uses monoethanolamine.Obtained have the insulating film pattern 40 of the 40a of pixel openings portion thereafter.This insulating film pattern 40 as shown in Figure 6, by the requirement setting that on the pattern of auxiliary distribution 30, also forms the auxiliary distribution contact formation 40b of portion.

Making pixel openings portion is 300 μ m * 300 μ m, and the contact formation 40b of portion of negative electrode and auxiliary distribution is 200 μ m * 200 μ m.Obtain negative electrode and separate pattern 50 thereafter.Adopt parallel flat RF plasma device, implement the oxygen plasma irradiation, carry out the surface modification of ITO film thereafter.Then adopt evaporation coating device, the mask evaporation organic EL layer 60 and negative electrode 70.Concrete way is that at oxygen flow 50sccm (50mL/min under the standard state), the total pressure 6.7Pa of gas under the plasma treatment condition of 1.5kW, has carried out the plasma treatment of 60 seconds RIE (reactive ion etching) mode.

Thereafter, formed the boundary layer of 10nm respectively by copper phthalocyanine (hereinafter referred to as CuPc) formation, 60nm by N, N '-two (naphthalene-1-yl)-N, N '-diphenyl-benzidine (the hole transporting layer that constitutes hereinafter referred to as α-NPD), the luminescent layer that constitutes by three (oxine) aluminium (being designated hereinafter simply as Alq) of 50nm, the electron injecting layer that constitutes by LiF of 0.5nm, the negative electrode that constitutes by Al of 200nm.

Wherein, the boundary layer that is constituting by CuPc, the hole transporting layer that constitutes by α-NPD, the luminescent layer that constitutes by Alq, in the electron injecting layer that constitutes by LiF, for forming the hole transporting layer of organic EL layer, can use the material of triphenyl diamines triphenylamines such as (hereinafter referred to as TPD) system to replace α-NPD.

Organic EL pattern 60 and negative electrode pattern 70 that organic EL layer constitutes have been formed thus.Thereafter, the periphery with ultraviolet curing resin seals 90 applying these organic EL display element and counter substrate 80.Concrete way is, fits on counter substrate and sneaked into film as catching the CaO of water material 100, is coated with ultraviolet curing resin at the periphery of organic EL display element with distributor, irradiation ultraviolet radiation then, two substrates of fitting.Ultraviolet curable resin uses Na ガ セ チ バ XNR5516.

At portion of terminal applying anisotropic conducting film, by it connect TCP thereafter.Concrete way is, at the temporary transient crimping anisotropic conducting film 110 of package terminal portion.The for example available Hitachi of anisotropic conducting film changes into system ANISOLM 7106U.Temporary transient crimping temperature is 80 ℃, and crimping pressure is 1.0MPa, and the crimping time is 5 seconds.

Then, the TCP with built-in driving circuit finally is crimped on splicing ear portion.Final crimping temperature is 170 ℃, and crimping pressure is 2.0MPa, and the crimping time is 20 seconds.The organic EL display element that produces like this can form low resistance and and the also low auxiliary distribution of contact resistance of negative electrode, and the good terminal of moisture-proof.

With the aforementioned same TEG of metal film that made as the application of layered product of the present invention, its wiring resistance is 0.14 Ω/.Film resistor during sputter is 0.11 Ω/.The contact resistance that is obtained by contact TEG is 0.5～0.8 Ω/200 μ m, burns at about 350mA metal pattern.

To be kept in the portion of terminal that this spr substrate does not encapsulate under 80 ℃, the hot and humid environment of 90%RH.As a comparison, to the situation of portion of terminal metal employing MoNb (10 atom %), Al, MoNb (10 atom %), carried out same evaluation.At this moment thickness is that MoNb is 70nm, and Al is 350nm.See Figure 15, Figure 16 through the etch state after 1000 hours.Here Figure 15 is the pattern of this routine laminated film, and Figure 16 is the laminated film that is formed by MoNb and Al.

As mentioned above as can be known, use laminated film of the present invention, compare with the situation that MoNb is used for coverlay, extent of corrosion reduces.The material that encapsulated through after 700 hours, is removed the FPC and the ACF of encapsulation, observe.The result is that extent of corrosion further reduces.

Excellent corrosion resistance when this means the NiMo alloy as coverlay.The lamination metal has formed under the situation of pattern, prevents that at the pattern end face Mo of Ni diffusion layer from exposing.If this Mo is replaced to higher metal of corrosion resistance such as MoNb, can prevent that then Ni is diffused among the Al, and can suppress corrosion.

The possibility of utilizing on the industry

As mentioned above, the layered product of the application of the invention can form the matrix that low resistance, pattern form the high band distribution of function admirable and moisture-proof, and use value is arranged very much.And, can make the display of high definition and high reliability.Particularly to seeking the distribution low resistanceization to prolong component life, the organic EL display element that improves the characteristics of luminescence is very useful.

Table 1

Reference example	Target is formed (quality %)	Thickness (nm)	Film resistor (Ω/)	Etching speed (nm/ second)	Moisture-proof (1)
						1	Ni	200	0.44	×	○
2	72.5Ni-24.5Mo-3Fe	118	10	0.7	○
						3	65Ni-32Mo-3Fe	114	11	1.8	○
4	Mo	200	0.75	6.7	×
						5	Al	167	0.27	1.5	○

Claims (28)

1. layered product, it is to form the layered product that the matrix of band distribution is used, and it is characterized in that, has being the conductor layer 1 of principal component and being the top layer of principal component with the Ni-Mo alloy on conductor layer 1 with Al or Al alloy on the matrix.

2, layered product as claimed in claim 1, its feature also are, between conductor layer 1 and matrix, begin to have ITO layer and substrate layer successively from the matrix side.

3, layered product as claimed in claim 2, its feature are that also the principal component of substrate layer is Mo or Mo alloy.

4, layered product as claimed in claim 2, its feature are that also substrate layer is a principal component with NiMo, and contain and be selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

5, layered product as claimed in claim 2, its feature are that also the containing ratio of the Ni in the substrate layer is 20～90 quality % of whole compositions, and the containing ratio of Mo is 10～80 quality % of whole compositions.

6, layered product as claimed in claim 1, its feature also be, between conductor layer 1 and top layer, have do not contain Ni prevent the Ni diffusion layer.

7, layered product as claimed in claim 6, its feature also are, prevent that the Ni diffusion layer from being principal component with Mo, do not contain Ni.

8, layered product as claimed in claim 6, its feature also are, prevent that the Ni diffusion layer from being MoNb, MoTa, MoV or MoW.

9, layered product as claimed in claim 6, its feature also are, prevent that the conductive material of Ni diffusion layer from containing Mo and Nb or Mo and Ta, and the containing ratio of Mo is 80～98 quality %, and the containing ratio of Nb or Ta is 2～20 quality %.

10, layered product as claimed in claim 1, its feature also be, top layer contains and is selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

11, layered product as claimed in claim 1, its feature are that also the containing ratio of the Ni in the top layer is 20～90 quality % of whole compositions, and the containing ratio of Mo is 10～80 quality % of whole compositions.

12, organic EL display element, it is to adopt organic EL display element that each described layered product forms in the claim 1～11, it is characterized in that, on matrix, have and electrode layer 1 (5) opposed electrode layer 2 (3), between electrode layer 1 (5) and electrode layer 2 (3), disposed organic EL layer, begun to have disposed successively matrix, conductor layer 1 and top layer from the matrix side.

13, organic EL display element, it is to have opposed electrode layer 1 and electrode layer 2 on matrix, between electrode layer 1 and electrode layer 2, disposed organic EL display element of organic EL layer, it is characterized in that, has the conductor layer 1 that is connected with electrode layer 1 conduction, upside at conductor layer 1 has top layer, and the principal component of conductor layer 1 is Al or Al alloy, and the principal component of top layer is the Ni-Mo alloy.

14, organic EL display element as claimed in claim 13, its feature also be, top layer contains and is selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

15, as claim 13 or 14 described organic EL display elements, its feature also is, between conductor layer 1 and top layer, have do not contain Ni prevent the Ni diffusion layer.

16, organic EL display element as claimed in claim 15, its feature also be, prevents that the Ni diffusion layer from being to be selected from any of MoNb, MoTa, MoV, MoW.

17, organic EL display element as claimed in claim 13, its feature also be, has the substrate layer that contains Mo or Mo alloy at the downside of conductor layer 1.

18, organic EL display element as claimed in claim 13, its feature is that also electrode layer 2 is the ITO layer.

19, the splicing ear of organic EL display element, it is the splicing ear that is used to connect organic EL display element of electrode layer 1 on the matrix that is configured in organic EL display element and drive circuit, it is characterized in that, have with Al or Al alloy is the conductor layer 1 of principal component, with conductor layer 1 upside be the top layer of principal component with the Ni-Mo alloy, by by the requirement forming circuit of drive circuit to electrode layer 1 input current.

20, the splicing ear of organic EL display element as claimed in claim 19, its feature also be, top layer contains and is selected from a kind of in oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon or oxygen and nitrogen and the carbon.

21, as the splicing ear of claim 19 or 20 described organic EL display elements, its feature also is, between conductor layer 1 and top layer, have do not contain Ni prevent the Ni diffusion layer.

22, laminated body manufacturing method, it is each described laminated body manufacturing method in the claim 1～11, it is characterized in that, forms the film of conductive layer 1 on matrix, forms the film of top layer then.

23, laminated body manufacturing method as claimed in claim 22, its feature also are, form the film of transparent conductor layer 2, form pattern, form the film of conductor layer 1 then.

24, as claim 22 or 23 described laminated body manufacturing method, its feature also is, when forming top layer, carries out the processing of oxidation, nitrogenize, oxynitriding, oxygen carbonization, nitrogen carbonization or the carbonization of oxygen nitrogen.

25, the band distribution matrix, it is characterized in that, in claim 1～11 on each described layered product with plane formation pattern.

26, the manufacture method of the splicing ear of each described organic EL display element in the claim 19～21, it is characterized in that, form the film of transparent conductor layer 2, behind the formation pattern, formation contains the laminated film of conductor layer 1 and top layer, forms pattern then on laminated film.

27, the manufacture method of each described organic EL display element in the claim 12～18, it is characterized in that, on matrix, form the film of transparent conductor layer 2, form the laminated film that contains conductor layer 1 and top layer then, with conductor layer 2 as electrode 2, adopt the mode of laminated film, the pattern of cambium layer press mold with at least a portion of distribution from conductor layer 1 to splicing ear.

28, the manufacture method of organic EL display element as claimed in claim 27, its feature also is, forms the film of transparent conductor layer 2 on matrix, behind electrode layer 2 formation patterns, the film by forming conductor layer 1 and the film of top layer and the cambium layer press mold forms pattern then on laminated film.

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